Hair preparation

ABSTRACT

A COMPOSITION SUITABLE FOR USE AS A HAIR PREPARATION IS PROVIDED WHICH MAY BE UNIFORMLY APPLIED TO THE HAIR, DRIES QUICKLY UPON APPLICATION TO FORM A FLEXIBLE FILM, IS EASILY REMOVED FROM THE HAIR WASHING IN THE USUAL MANNER WITH SOAP AND WATER, AND MAY BE FORMULATED TO PROVIDE A DEGREE OF CURL RETENTION SUITABLE FOR A WIDE RANGE OF SPECIFIC HAIR SETTING CONDITIONS. THE COMPOSITION COMPRISES AT LEAST ONE SULFATED ALKALI CELLULOSE ETHER IN A SOLVENT MIXTURE COMPRISING AT LEAST 60% BY WEIGHT OF AN ALCOHOL AND 0 TO 40% BY WEIGHT OF WATER. PREFERABLY, THE COMPOSITION COMPRISES AT LEAST ONE SULFATED ALKALI ETHER RESIN CHOSEN FROM THE GROUP CONSISTING OF ALKYL ETHERS, HYDROXYALKYL ETHERS AND HYDROXYALKYL ALKYL ETHERS, WHERE IN EACH OF THE ALKYL AND HYDROXYALKYL GROUPS CONTAINS NO MORE THAN FOUR CARBON ATOM. THE COMPOSITION, WHEN COMBINED WITH AN AEROSOL PROPELLANT SYSTEM, MAY BE APPLIED AS A HAIR SPRAY.

3,741,783 HAIR PREPARATION Deger Tunc, Edison, N.J., assignor to Johnson & Johnson No Drawing. Filed May 3, 1971, Ser. No. 139,858 Int. Cl. C08h 17/34 U.S. Oi. 106-189 15 Claims ABSTRACT OF THE DISCLOSURE A composition suitable for use as a hair preparation is provided which may be uniformly applied to the hair, dries quickly upon application to form a flexible film, is easily removed from the hair by washing in the usual manner with soap and water, and may be formulated to provide a degree of curl retention suitable for a wide range of specific hair setting conditions. The composition comprises at least one sulfated alkali cellulose ether in a solvent mixture comprising at least 60% by weight of an alcohol and to 40% by weight of water. Preferably, the composition comprises at least one sulfated alkali ether resin chosen from the group consisting of alkyl ethers, hydroxyalkyl ethers and hydroxyalkyl-alkyl ethers, wherein each of the alkyl and hydroxyalkyl groups contains no more than four carbon atoms. The composition, when combined with an aerosol propellant system, may be applied as a hair spray.

BACKGROUND OF THE INVENTION This invention concerns a composition suitable for use as a preparation for styling and setting hair which, when applied, will dry quickly, may be easily removed by washing with soap and Water, and can be tailored, with respect to its curl retention properties, to suit a specific hair setting condition. In a preferred embodiment, the composition is combined with a suitable aerosol propellant system and is useful as a hair spray which, in addition to having a fast drying rate, variable curl retention properties and excellent washing characteristics, may be uniformly applied.

While the present invention is described herein in terms of a composition for styling and controlling human hair, it will be clear to those skilled in the art that the invention is not limited thereto but rather encompasses many other uses in which the properties hereinafter described as appertaining to this invention are advantageous.

Many hair preparations are already available comprising a film-forming resin dessolved in a solvent and provided with an aerosol system for spraying onto the hair, whereafter the solvent evaporates leaving behind a resinous film which holds the hair in place. Several drawbacks have been encountered with such prior preparations in that, while ideally the resin used should exhibit certain properties, these properties are rarely found in combination. For example, the hair spray should dry quickly when applied and be easily removed when the hair is normally washed with soap and water, i.e., the filmforming resin should be both soluble in a highly volatile solvent such as an alcohol as well as soluble in water to the extent necessary to remove the film from the hair. Many resins, however, though readily soluble in water and otherwise suitable for use in hair preparations such as, for example, carboxy methylcellulose and hydroxypropyl ethylcellulose, tend to be insoluble in alcohol or soluble only in solutions containing minor proportions of alcohol, the remainder being water. Such primarily watercontaining solutions are highly disadvantageous as they tend to wet the hair and dry slowly. On the other hand, other resins such as ethylcellulose ether do dissolve easily into alcohol solvents but tend to be insoluble or only slightly solube in water.

United States Patent O 3,741,783 Patented June 26, 1973 ice To have satisfactory curl retention properties a resin should form films exhibiting high tensile strength and good resistance to the plasticizing effects of high humidity. At the same time, it is desirable that the resin, in solution, exhibit a low viscosity so that the solution can be easily and uniformly applied. These criteria are in conflict, as those resins which form strong films tend to be highly viscous in solution. Further, because the curl retention ability of a particular resin changes with such factors as the varying nature of human hair and the varying conditions of humidity from place to place and from season to season, resin suitable for one specific hair setting condition are not easily modified for use at another condition.

In addition to the above-described solubility, viscosity and film strength characteristics, a suitable resin should form films which are nontacky, clear, have good antistatic properties, and be compatible with aerosol propellants when used as a spray or with other additives such as perfumes, lubricants, emollients or the like. Finally, the resin should lend itself to storage in solution form for a reasonable length of time and be capable of being produced commercially.

While a great number of various resins and resin combinations have been used heretofore, these have represented compromises in that, while meeting some of the above-described criteria, they each have fallen short of others.

SUMMARY OF THE INVENTION In accordance with this invention, a composition is provided which may be uniformly applied to the hair, dries quickly upon application, forms a film of high tensile strength with high curl rentention even under conditions of high humidity, and is easily removed from the hair by washing in the usual manner with soap and Water. The composition comprises at least one sulfated alkali cellulose ether in a solution comprising at least about 60% by weight of an alcohol and 0 to about 40% by weight of water. Preferably, the composition comprises at least one sulfated alkali cellulose ether resin chosen from the group consisting of alkyl ethers, hydroxylalkyl ethers and hydroxy-alkyl ethers, wherein each of the alkyl and hydroxyalkyl groups contains no more than four carbon atoms.

The curl retention property of the films formed by the resins herein prescribed is varied by varying the degree of sulfate substitution (hereinafter D.S.) which expresses the average number of sulfate groups per anhydroglucose unit of the cellulose derivative. A D.S. ranging from about 0.15 to about 0.7 is suitable in a hair spray and will produce films adequately varying in curl retention power to suit the various conditions of hair types and relative humidities usually encountered.

In a preferred embodiment of this invention, an alkali ethylcellulose sulfate ether is used as the resin in an anhydrous solution of an alcohol, this resin being soluble in both pure alcohol and pure water.

While the resinous films may be cast upon the hair by applying the compositions of this invention with a brush, comb or other suitable applicator, preferably the compositions are combined with an aerosol propellant system and applied as a spray. The compositions prescribed herein are completely compatible with such commonly used aerosol propellants as the halogenated hydrocarbon aerosol system and hence are admirably suitable for use as hair spray compositions. Additionally, they may be combined with such additives as perfumes, emollients, lubricants and the like.

DETAILED DESCRIPTION OF THE INVENTION The sulfated cellulose ethers of this invention may be produced by first forming the ether derivatives of cellulose and then sulfating with a suitable sulfating agent. The ethers are generally prepared by reacting a purified form of cellulose with either an alkyl halide, an alkylene oxide or both to form either the alkyl ether, the hydroxyalkyl ether or the hydroxyalkyl-alkyl ether, respectively. Unsulfated cellulose ethers are presently available as, for example, the methylcellulose and hydroxypropyl methylcellulose ethers sold under the trademark Methocel and the ethylcellulose ethers sold under the trademark Etho cel, all available from the Dow Chemical Company, Inc., of Midland, Mich., as well as the hydroxy ethylcellulose ethers available from Hercules, Incorporated, and the Union Carbide Corporation under the trademarks Natrosol and Cellosize, respectively.

Table 1 below illustrates properties of typical ethers suitable for sulfating and use in accordance with this invention:

propylene glycol ether.

1 5% Ethocel Std. in 80/20 toluene/ethanol at 25 C. 5% Ethocel Med. in 60/40 toluene/ethanol at 25 C.

The average number of alkyl groups per anhydroglucose unit. 3 2% aqueous solution at 20 C.

The ethers may be sulfated in accordance with a process described by W. D. Slowig and M. E. Rowley in Textile Research Journal, volume 38, Number 9, September 1968, whereby an alkali sulfating agent is prepared by reacting acetic anhydride with sulfuric acid and an alkali sulfate, all in an acetic acid solution, to form alkali acetyl sulfate. The alkali acetyl sulfate is then reacted with the cellulose ether to yield the alkali cellulose sulfate ether resin used herein.

It has been discovered that by sulfating alkali cellulose ethers of the kind herein described, their suitability as resins for hair preparations and particularly for hair sprays is greatly increased. For example, ethylcellulose ether, while soluble in alcohol solutions, is essentially insoluble in water and, as such, is entirely unsatisfactory for use as a hair preparation. However, when in accordance with this invention the ethylcellulose ether is converted to potassium ethylcellulose sulfate, the resin is rendered almost completely soluble in water as well as in alcohol and is aptly suited for use in hair preparations.

In accordance with this invention, the alkali cellulose sulfate ether resins herein prescribed are dissolved in a solvent solution having an alcohol content of at least about 60% by weight and a water content of from to about 40% by weight. The alcohol used is one which will dry quickly upon application, be compatible with any additives and have a minimal corrosive effect on the metal containers ordinarily used for hair sprays. Suitable alcohols are the lower alkyl alcohols, ethanol and isopropanol being the alcohols of choice.

The proportions of resin to solvent mixture are limited, on the one hand, by the need for obtaining suitable drying rates upon application, and on the other, by the viscosity of the resin solution. A low resin concentration will require the application of a large volume of solution to deposit a sutficient quantity of resin on the hair and hence will require an unacceptably long drying time to evaporate the solvent. Additionally, the number of hair applications per unit volume of solution would be disadvantageously reduced. On the other hand, too great a resin concentration will result in a solution which is too viscous to be uniformly applied. Accordingly, the resin concentration should vary from about 0.5 to about 5 grams of resin per 100 grams of solvent mixture and preferably from about 1 to about 4 grams per 100 grams.

All the resins prescribed herein are soluble to the extent of at least 3 grams of resin in grams of a solvent mixture comprising at least 60% alcohol and 40% water on a Weight basis. From the point of view of accelerating the rate of drying, it is advantageous that a specific resin be dissolved in a solvent mixture having the greatest conconcentration of alcohol commensurate with the ability of that solvent mixture to dissolve the resin in the abovedescribed quantities. For this reason, the preferred com position comprises alkali ethylcellulose sulfate ether, which is soluble in a pure ethanol or isopropanol solvent to the extent of more than 2 grams of resin per gram of solvent.

It has been discovered that the curl-retaining property of the films formed by the herein-prescribed resins varies witht he D.S. of the resin. As the D.S. of the resin increases, there is a decrease in the curl-retaining power of the resin. On the other hand, with increasing D.S., the water solubility of the resin is increased. This unique property of the sulfated resins allows for the formulation of a hair preparation to suit the particular conditions at which it is to be applied. Accordingly, the D.S. should vary from about 0.15 to about 0.7 and preferably should vary from about 0.2 to about 0.5, the choice of a particular D.S. depending upon the anticipated application conditions. The D.S. may be controlled by varying the reaction time during the sulfating of the cellulose ether, by varying the quantity of sulfating agent used or by a combination of such methods.

The hair preparations of this invention are compatible with a wide variety of additives usually incorporated into hair preparations. For example, oils and lubricants such as isopropyl palmitate and castor oil may be incorporated and are fully compatible, as are other additives such as perfumes, emollients, plasticizers and penetrants.

It is particularly important that the resin solutions be compatible with the halogenated hydrocarbon aerosol propellants such as, for example, trichloro-trifluoro hydrocarbons, dichloro-difluoro hydrocarbons and mixtures thereof. The alcohol resins mixtures are completely miscible with these aerosols.

To more completely describe the hair preparations of this invention, the following examples are given:

Example 1 A sulfating agent, sodium acetyl sulfate, is prepared by combining the following ingredients:

The sodium sulfate is first added to a mixture of the acetic anhydride and acetic acid at room temperature, the sulfuric acid then being added at a rate such that the temperature of the mixture does not exceed 54.4 C. The resulting solution if acidic is then neutralized by adding small increments of additional sodium sulfate and then cooling to 4.4 C. and filtering.

Ethocel Std., a trademark of the Dow Chemical Company for ethylcellulose ether, is dissolved in acetic acid in a proportion of 45.4 parts by weight of resin in parts of acetic acid. Ethocel Std. has a degree of ethyl substitution of 2.25 to 2.58, and a 5% by weight solution of the resin dissolved in a solvent mixture of toluene and ethylene in the proportions of 80 to 20 parts by weight, respectively, and measured at 25 C. has a viscosity of 7 to 1000 cps. The resin is dissolved in the acetic acid by mixing, in a jacketed, sigma blade mixer, for about 30 minutes at a jacket temperature of 38 C. The jacket temperature is then dropped to 15 C. and held at that temperature until the reaction mixture has cooled to 21 C.

The sulfating solution is then added incrementally over a period of 14 to 20 minutes, taking care not to exceed a reaction temperature of 32 C. A mixture consisting of 0.7 part by weight of sodium acetate in 6 parts by weight of anhydrous isopropanol is added 40 minutes after starting the addition of the sulfating mixture. After stirring for 5 minutes, 160 parts by weight of isopropanol at 5 C. is stirred in to initiate precipitation. The liquid phase is then decanted and the wet product is ground in a Fitzmill grinder and then washed with isopropanol until an essentially neutral wash is obtained, whereupon neutralization is completed by adding a methanolic sodium hydroxide solution to obtain a Wash having a pH of 7 to 8.

The resulting resin has a degree of sulfate substitution of about 0.43. Ten grams of resin are completely dissolved in 90 grams of alcohol and a film cast on a substrate, by applying thereto the alcohol solution and allowing the alcohol to evaporate, will break up and dissolve upon being submerged in water at a temperature of 25 Example 2 Partially sulfated sodium methylcellulose ether is prepared from Methocel MC, a trademark of Dow Chemical Co., Inc., for methylcellulose ether having a degree of methyl substitution of 1.64 to 1.92 and a viscosity of 10 to 4000 cps when a 2% aqueous solution is measured at C. The sulfating is carried out following the procedure described in Example 1 using the sulfating agent prepared in accordance with that example.

The resulting resin has a degree of sulfate substitution of 0.29. Two grams of resin are completely dissolved in 100 grams of a 65.32327 weight by weight alcohol-water solution and a film cast on a substrate, by applying thereto the alcohol-water solution and allowing the solution to evaporate, will break up upon being submerged in water at a temperature of C.

Example 3 Partially sulfated sodium hydroxypropylmethylcellulose ether is prepared from a hydroxypropyl methylcellulose ether having a methyl substitution of 27 to 30% by weight and a hydroxypropyl substitution of 4 to 12% by weight. The sulfating is carried out following the procedure described in Example 1 using the sulfating agent prepared in accordance with that example.

The resulting resin has a degree of sulfate substitution of 0.285. Two grams of resin are completely dissolved in 100 grams of a 65.3:32.7 weight by weight alcoholwater-solution and a film cast on a substrate, by applying thereto the alcohol-water solution and allowing the solution to evaporate, will break up upon being submerged in water at a temperature of 25 C.

Example 4 A hair spray is prepared using the resin of Example 1 by combining the following ingredients:

The resin is first dissolved in the ethanol and the perfume is then added. The resulting homogenous solution is then combined with an equal part by weight of an aerosol propellant mixture consisting of 50% by weight of Genetron-ll and 50% by weight of Genetron-12, tradeamrks of the Allied Chemical Co. for trichloromonofluoro methane and dichloro-difluoro methane, respectively. The solution and the aerosol propellant form a homogenous mixture in an aerosol dispenser.

The spray, applied to hair swatches, goes on uniformly, dries rapidly, leaves a transparent, glossy, flexible, thin film and easily washes out with soap and water. The curl retention ability is tested as follows:

Hair swatches of Remi-Blue European hair measuring 25.4 cm. in length and weighing approximately 10 grams are washed with a commercial shampoo, thoroughly rinsed with distilled water and dried and then suspended on a motor chuck which is adjusted to rotate at a constant speed of 20 revolutions per minute. The ends of the swatches are weighted with a IO-gram clip to prevent motion of the hair during spraying. With the hair rotating, the spray is applied for a period of 10 seconds at a distance of 15 cm. The moist swatches are then wound on a rod into a curl and secured with a hair clip. The curls are then dried at 60 C. for 30 minutes and then conditioned for 16 hours at a temperature of 22 C. and a relative humidity of 50%. After conditioning, the rods are removed and the curls are placed on retention panels, the initial curl length being recorded. The panels are then placed vertically in a constant relative humidity chamber at a temperature of 22 C. and a relative humidity of Curl length is measured periodically during ex posure in the chamber. Curl retention is expressed in accordance with the following relationship:

Percent curl retention= where L=length of fully extended hair swatch (25.4 cm.), L,,=length of curl before exposure, and L =lengtl1 of curl after t hours of exposure.

The curls tested with the hair spray of this example exhibited a 65% curl retention after 6 hours of exposure.

Example 5 A hair spray is prepared with the sodium methylcellulose sulfate resin of Example 2 by combining the following ingredients in the same manner as Example 4:

The resulting homogenous solution is then combined in the manner of Example 4 with an equal part by weight of a propellant consisting of 50% by weight of Genetron- 114, a trademark of the Allied Chemical Co. for dichlorotetrafluoro ethane and 50% by weight of the aforesaid Genetron-12. This spray, applied to hair swatches, goes on uniformly and dries rapidly, although at a somewhat slower rate than that of the previous example. The film formed on the hair is transparent, glossy and flexible and is easily washed out with soap and water. A 74.6% curl retention was noted after 6 hours of exposure to a 76% relative humidity at a temperature of 22 C.

Example 6 A hair spray is prepared with the sodium hydroxypropyl methylcellulose resin of Example 3 by combining the following ingredients in the manner of Example 4:

Component: Parts by weight Sodium hydroxypropyl methylcellulose sulfate v 2.0 Perfume 0.3 Water 32.7 Ethanol 65.0

7 To illustrate the eifects of the degree of sulfate substitution of the resin upon the curl retention properties of the resulting sprays, the following example is given:

Example 7 A series of sodium ethylcellulse sulfate resins are synthesized in accordance with the procedures of Example 1 with the exception that varying quantities of sulfating agent are used to produce resins of varying D.S., as shown in Table 2 below. Each of these resins is then incorporated into a hair spray using the proportions and procedures of Example 4 and the percent curl retention is determined for each spray, using the method of Example 4 at a chamber temperature of 22 C. and a relative humidity of about 85% TABLE 2 Fraction of sul- Percent fating cur agent reten- Film solubility of Ex. 1 D.S tlon in water at 22 C.

1. 0.43 51 Soluble. 0.8 0.34 63 Do. 0. 6 0.28 66 Do. 0. 5 0. 22 73 Do. 0. 4 0. 16 Not completely soluble but s film breaks up.

i After 6 hours of exposure to 85% R41.

Table 2 indicates that the curl retention may be increased by decreasing the D.S'. of the resin used in the spray up to the point at which the resinous films are relatively insoluble in water and, accordingly, a spray may be prepared to accommodate diflicult hair setting conditions of high humidity by simply decreasing the degree of sulfation.

'It will be understood by those skilled in the art that variations and modifications of the specific examples and descriptions given above may be employed without departing from the scope of the invention as defined in the appended claims.

What is claimed is:

1. An aerosol preparation comprising at least one sulfated alkali cellulose ether resin chosen from the group consisting of alkali alkyl cellulose sulfate, alkali hydroxyalkyl cellulose sulfate, and alkali hydroxyalkyl-alkyl cellulose sulfate wherein each of said alkyl and hydroxyalkyl groups contain no more than 4 carbon atoms; said ether dissolved in a solvent mixture comprising at least 60 percent by weight of an alcohol and 0 to about 40 percent by weight of water; said hair preparation further comprising an aerosol propellant.

2. The hair preparation of claim 1 wherein the resins are present in a proportion of about 0.5 to about 5 grams of resin per 100 grams of solvent mixture.

3. The hair preparation of claim 1 wherein the resins have a degree of sulfate substitution of from about 0.15 to about 0.7.

4. The hair preparation of claim 3 wherein the resins have a degree of sulfate substitution of from about 0.2 to about 0.5.

5. The hair preparation of claim 3 wherein the resin is an alkali hydroxypropyl methylcellulose sulfate ether.

6. The hair preparation of claim 3 wherein the resin is an alkali methylcellulose sulfate ether.

7. The hair preparation of claim 3 wherein the resin is an alkali ethylcellulose sulfate ether.

8. The hair preparation of claim 7 wherein the solvent mixture comprises about 100% alcohol by weight and about 0% water by weight.

9. The hair preparation of claim 1 wherein the alcohol is a lower alkylalcohol. p

10. The hair preparation of claim 9 wherein the alcohol is ethanol.

11. The hair preparation of claim 9 wherein the alcohol is isopropanol.

12. A hair spray comprising an alkali ethylcellulose sulfate ether resin having a degree of sulfate substitution of from about 0.15 to about 0.7, dissolved in a lower alkyl alcohol solvent in the proportions of about 0.5 to about 5 grams of resin per 100 grams of alcohol and further comprisingan aerosol propellant.

13. A method of treating hair by applying thereto a solution comprising at least one sulfated alkali cellulose ether resin chosen from the group consisting of alkali alkyl cellulose sulfate, alkali hydroxyalkyl cellulose sulfate, and alkali hydroxyalkyl-alkyl cellulose sulfate, wherein each of said alkyl and hydroxyalkyl groups contains no more than four carbon atoms; said ethers dissolved in a solvent mixture comprising at least percent by weight of alcohol and 0 to about 40 percent by weight of water; and allowing said solvent mixture to evaporate leaving a resinous film.

14. The method of claim 13 for treating hair in difiicult setting conditions wherein the sulfated alkali cellulose ether resin is one having a low degree of sulfation.

15. The method of claim 13 for treating hair in mild hair setting conditions wherein the sulfated alkali cellulose ether resin is one having a high degree of sulfation.

References Cited UNITED STATES PATENTS 3,478,016 11/1969 Rowley 260-231 R 2,857,314 10/1958 Philips 106197 R 2,422,000 6/ 1947 Dickey 260-231 A OTHER REFERENCES Chem. Abst.,' 54:22,l20h.

THEODORE MORRIS, Primary Examiner US. (:1. xx.

$32333? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 337 ,7 3 Dated June 26,1973

Inventor(s) Deger Tune It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

r- In Column 1, line 72, "solube" should read soluble In Column 2, line +2, "hydroxy-alkyl" should read hydroxyalkyl-alkyl In Column L, line 5, delete "con'I. In Column line 1 "witht he" shouldread with the In Column 5, line 21, "tradeamrks" should read trademarks In Column 7, line +1, "An aerosol preparation" should read An aerosol hair preparation Signed and sealed this 2nd day of April 1.9714.

(SEAL) Attest:

EDWARD M.FLETCHER, JR. 1 C MARSHALL DANN I Attesting Officer Commissioner of Patents 

